Abstract:

The present invention relates to electrically conductive polymer
compositions, and their use in electronic devices. The compositions are
an aqueous dispersion of at least one electrically conductive polymer
doped with a non-fluorinated polymeric acid, at least one high-boiling
polar organic solvent, and an additive selected from the group consisting
of fullerenes, carbon nanotubes, and combinations thereof.

3. The dispersion of claim 2, wherein the electrically conductive polymer
is selected from the group consisting of a polyaniline, polythiophene, a
polypyrrole, a polymeric fused polycyclic heteroaromatic, copolymers
thereof, and combinations thereof.

4. The dispersion of claim 3, wherein the electrically conductive polymer
is selected from the group consisting of unsubstituted polyaniline,
poly(3,4-ethylenedioxythiophene), unsubstituted polypyrrole,
poly(thieno(2,3-b)thiophene), poly(thieno(3,2-b)thiophene), and
poly(thieno(3,4-b)thiophene).

6. The dispersion of claim 5 wherein the polymeric sulfonic acid is
selected from the group consisting of poly(styrenesulfonic acid),
poly(2-acrylamido-2-methyl-1-propanesulfonic acid) and mixtures thereof.

7. The dispersion of claim 1 wherein the amount of doped conducting
polymer in the composite dispersion is in the range of from 0.1% to 5% by
weight based on the total weight of the dispersion.

8. The dispersion of claim 1 wherein an additive is a fullerene.

9. The dispersion of claim 8 wherein the fullerene is selected from the
group consisting of C60, C60-PCMB, C70, C70-PCBM, and combinations
thereof.

10. The dispersion of claim 1 wherein the amount of additive present is in
the range of from 0.2% to 50% by weight based on the total weight of the
dispersion.

11. The dispersion of claim 1 wherein the solvent has a boiling point of
at least 120.degree. C.

12. The dispersion of claim 1 wherein the solvent is present in the
composite dispersion in the range of from 1% to 15% by weight based on
the total weight of the dispersion.

13. The dispersion of claim 1 having a pH greater than 2.

14. A film made from the dispersion of claim 1.

15. The film of claim 14 having a conductivity of at least 100 S/cm.

16. An electronic device comprising at least one layer made from the
dispersion of claim 1.

17. The device of claim 16, wherein the layer is an anode.

18. The device of claim 16, wherein the layer is a buffer layer.

Description:

RELATED APPLICATION DATA

[0001]This application claims priority under 35 U.S.C. § 119(e) from
U.S. Provisional Application No. 60/938,786 filed on May 18, 2007, which
is incorporated by reference herein in its entirety.

BACKGROUND INFORMATION

[0002]1. Field of the Disclosure

[0003]This disclosure relates in general to aqueous dispersions of
electrically conductive polymers containing solvent and additives, and
their use in electronic devices.

[0004]2. Description of the Related Art

[0005]Electronic devices define a category of products that include an
active layer. Organic electronic devices have at least one organic active
layer. Such devices convert electrical energy into radiation such as
light emitting diodes, detect signals through electronic processes,
convert radiation into electrical energy, such as photovoltaic cells, or
include one or more organic semiconductor layers.

[0006]Organic light-emitting diodes (OLEDs) are an organic electronic
device comprising an organic layer capable of electroluminescence. OLEDs
containing conducting polymers can have the following configuration:
[0007]anode/buffer layer/EL material/cathodewith additional layers
between the electrodes. The anode is typically any material that has the
ability to inject holes into the EL material, such as, for example,
indium/tin oxide (ITO). The anode is optionally supported on a glass or
plastic substrate. EL materials include fluorescent compounds,
fluorescent and phosphorescent metal complexes, conjugated polymers, and
mixtures thereof. The cathode is typically any material (such as, e.g.,
Ca or Ba) that has the ability to inject electrons into the EL material.
Electrically conducting polymers having low conductivity in the range of
10-3 to 10-7 S/cm are commonly used as the buffer layer in
direct contact with an electrically conductive, inorganic oxide anode
such as ITO.

[0008]Electrically conducting polymers which have the ability to carry a
high current when subjected to a low electrical voltage, may have utility
as electrodes for electronic devices. However, many conductive polymers
have conductivities which are too low for use as electrodes. Furthermore,
the mechanical strength of films made from the polymers, either
self-standing or on a substrate, may not be sufficient for the electrode
applications.

[0009]Accordingly, there is a continuing need for improved conducting
polymer compositions.

SUMMARY

[0010]There is provided an aqueous dispersion comprising at least one
electrically conductive polymer doped with at least one non-fluorinated
polymeric acid polymer, a high-boiling polar solvent, and an additive
selected from the group consisting of carbon fullerenes, nanotubes, and
combinations thereof.

[0011]In another embodiment, there is provided a film formed from the
above dispersion.

[0012]In another embodiment, electronic devices comprising at least one
layer comprising the above film are provided.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013]The invention is illustrated by way of example and not limitation in
the accompanying figures.

[0015]Skilled artisans will appreciate that objects in the figures are
illustrated for simplicity and clarity and have not necessarily been
drawn to scale. For example, the dimensions of some of the objects in the
figures may be exaggerated relative to other objects to help to improve
understanding of embodiments.

DETAILED DESCRIPTION

[0016]There is provided an aqueous dispersion of at least one electrically
conductive polymer doped with at least one non-fluorinated polymeric
acid, at least one high-boiling polar organic solvent, and an additive
selected from the group consisting of carbon fullerenes, nanotubes, and
combinations thereof. The above dispersion is referred to herein as the
"new composition" and the "composite dispersion".

[0017]Many aspects and embodiments are described herein and are merely
exemplary and not limiting. After reading this specification, skilled
artisans will appreciate that other aspects and embodiments are possible
without departing from the scope of the invention.

[0018]Other features and benefits of any one or more of the embodiments
will be apparent from the following detailed description, and from the
claims. The detailed description first addresses Definitions and
Clarification of Terms followed by the Doped Electrically Conductive
Polymer, the Solvent, the Additive, Preparation of the Doped Electrically
Conductive Polymer Composition, Buffer Layers, Electronic Devices, and
finally, Examples.

1. DEFINITIONS AND CLARIFICATION OF TERMS USED IN THE SPECIFICATION AND
CLAIMS

[0019]Before addressing details of embodiments described below, some terms
are defined or clarified.

[0020]The term "conductor" and its variants are intended to refer to a
layer material, member, or structure having an electrical property such
that current flows through such layer material, member, or structure
without a substantial drop in potential. The term is intended to include
semiconductors. In some embodiments, a conductor will form a layer having
a conductivity of at least 10-7 S/cm.

[0021]The term "electrically conductive" as it refers to a material, is
intended to mean a material which is inherently or intrinsically capable
of electrical conductivity without the addition of carbon black or
conductive metal particles.

[0022]The term "polymer" is intended to mean a material having at least
one repeating monomeric unit. The term includes homopolymers having only
one kind, or species, of monomeric unit, and copolymers having two or
more different monomeric units, including copolymers formed from
monomeric units of different species.

[0023]The term "acid polymer" refers to a polymer having acidic groups.

[0024]The term "acidic group" refers to a group capable of ionizing to
donate a hydrogen ion to a Broonsted base.

[0025]The term "highly-fluorinated" refers to a compound in which at least
90% of the available hydrogens bonded to carbon have been replaced by
fluorine.

[0026]The terms "fully-fluorinated" and "perfluorinated" are used
interchangeably and refer to a compound where all of the available
hydrogens bonded to carbon have been replaced by fluorine.

[0027]The term "polar" refers to a molecule that has a permanent electric
dipole.

[0028]The term "high-boiling solvent" refers to an organic compound which
is a liquid at room temperature and has a boiling point of greater than
100° C.

[0029]The term "doped" as it refers to an electrically conductive polymer,
is intended to mean that the electrically conductive polymer has a
polymeric counterion to balance the charge on the conductive polymer.

[0030]The term "doped conductive polymer" is intended to mean the
conductive polymer and the polymeric counterion that is associated with
it.

[0031]The term "layer" is used interchangeably with the term "film" and
refers to a coating covering a desired area. The term is not limited by
size. The area can be as large as an entire device or as small as a
specific functional area such as the actual visual display, or as small
as a single sub-pixel. Layers and films can be formed by any conventional
deposition technique, including vapor deposition, liquid deposition
(continuous and discontinuous techniques), and thermal transfer.

[0032]The term "carbon nanotube" refers to an allotrope of carbon having a
nanostructure where the length-to-diameter ratio exceeds one million.

[0033]The term "fullerene" refers to cage-like, hollow molecules composed
of hexagonal and pentagonal groups of carbon atoms. In some embodiments,
there are at least 60 carbon atoms present in the molecule.

[0034]The term "nanoparticle" refers to a material having a particle size
less than 100 nm. In some embodiments, the particle size is less than 10
nm. In some embodiments, the particle size is less than 5 nm.

[0035]The term "aqueous" refers to a liquid that has a significant portion
of water, and in one embodiment it is at least about 40% by weight water;
in some embodiments, at least about 60% by weight water.

[0036]The term "hole transport" when referring to a layer, material,
member, or structure, is intended to mean such layer, material, member,
or structure facilitates migration of positive charges through the
thickness of such layer, material, member, or structure with relative
efficiency and small loss of charge.

[0037]The term "electron transport" means when referring to a layer,
material, member or structure, such a layer, material, member or
structure that promotes or facilitates migration of negative charges
through such a layer, material, member or structure into another layer,
material, member or structure.

[0038]Although light-emitting materials may also have some charge
transport properties, the terms "hole transport layer, material, member,
or structure" and "electron transport layer, material, member, or
structure" are not intended to include a layer, material, member, or
structure whose primary function is light emission.

[0039]The term "organic electronic device" is intended to mean a device
including one or more semiconductor layers or materials. Organic
electronic devices include, but are not limited to: (1) devices that
convert electrical energy into radiation (e.g., a light-emitting diode,
light emitting diode display, diode laser, or lighting panel), (2)
devices that detect signals through electronic processes (e.g.,
photodetectors photoconductive cells, photoresistors, photoswitches,
phototransistors, phototubes, infrared ("IR") detectors, or biosensors),
(3) devices that convert radiation into electrical energy (e.g., a
photovoltaic device or solar cell), and (4) devices that include one or
more electronic components that include one or more organic semiconductor
layers (e.g., a transistor or diode).

[0040]As used herein, the terms "comprises," "comprising," "includes,"
"including," "has," "having" or any other variation thereof, are intended
to cover a non-exclusive inclusion. For example, a process, method,
article, or apparatus that comprises a list of elements is not
necessarily limited to only those elements but may include other elements
not expressly listed or inherent to such process, method, article, or
apparatus. Further, unless expressly stated to the contrary, "or" refers
to an inclusive or and not to an exclusive or. For example, a condition A
or B is satisfied by any one of the following: A is true (or present) and
B is false (or not present), A is false (or not present) and B is true
(or present), and both A and B are true (or present).

[0041]Also, use of "a" or "an" are employed to describe elements and
components described herein. This is done merely for convenience and to
give a general sense of the scope of the invention. This description
should be read to include one or at least one and the singular also
includes the plural unless it is obvious that it is meant otherwise.

[0042]Group numbers corresponding to columns within the Periodic Table of
the elements use the "New Notation" convention as seen in the CRC
Handbook of Chemistry and Physics, 81st Edition (2000-2001).

[0043]Unless otherwise defined, all technical and scientific terms used
herein have the same meaning as commonly understood by one of ordinary
skill in the art to which this invention belongs. In the Formulae, the
letters Q, R, T, W, X, Y, and Z are used to designate atoms or groups
which are defined within. All other letters are used to designate
conventional atomic symbols. Group numbers corresponding to columns
within the Periodic Table of the elements use the "New Notation"
convention as seen in the CRC Handbook of Chemistry and Physics,
81st Edition (2000).

[0044]To the extent not described herein, many details regarding specific
materials, processing acts, and circuits are conventional and may be
found in textbooks and other sources within the organic light-emitting
diode display, lighting source, photodetector, photovoltaic, and
semiconductive member arts.

2. DOSED ELECTRICALLY CONDUCTIVE POLYMERS

[0045]The doped electrically conductive polymer has a polymeric counterion
derived from a polymeric acid to balance the charge on the conductive
polymer.

a. Electrically Conductive Polymer

[0046]Any electrically conductive polymer can be used in the new
composition. In some embodiments, the electrically conductive polymer
will form a film which has a conductivity greater than 0.1 S/cm. In some
embodiments, the new compositions described herein can be used to form
films having a conductivity greater than 100 S/cm.

[0047]The conductive polymers suitable for the new composition are made
from at least one monomer which, when polymerized alone, forms an
electrically conductive homopolymer. Such monomers are referred to herein
as "conductive precursor monomers." Monomers which, when polymerized
alone form homopolymers which are not electrically conductive, are
referred to as "non-conductive precursor monomers." The conductive
polymer can be a homopolymer or a copolymer. Conductive copolymers
suitable for the new composition can be made from two or more conductive
precursor monomers or from a combination of one or more conductive
precursor monomers and one or more non-conductive precursor monomers.

[0048]In some embodiments, the conductive polymer is made from at least
one conductive precursor monomer selected from thiophenes, pyrroles,
anilines, and polycyclic aromatics. The term "polycyclic aromatic" refers
to compounds having more than one aromatic ring. The rings may be joined
by one or more bonds, or they may be fused together. The term "aromatic
ring" is intended to include heteroaromatic rings. A "polycyclic
heteroaromatic" compound has at least one heteroaromatic ring.

[0049]In some embodiments, the conductive polymer is made from at least
one precursor monomer selected from thiophenes, selenophenes,
tellurophenes, pyrroles, anilines, and polycyclic aromatics. The polymers
made from these monomers are referred to herein as polythiophenes,
poly(selenophenes), poly(tellurophenes), polypyrroles, polyanilines, and
polycyclic aromatic polymers, respectively. The term "polycyclic
aromatic" refers to compounds having more than one aromatic ring. The
rings may be joined by one or more bonds, or they may be fused together.
The term "aromatic ring" is intended to include heteroaromatic rings. A
"polycyclic heteroaromatic" compound has at least one heteroaromatic
ring. In some embodiments, the polycyclic aromatic polymers are
poly(thienothiophenes).

[0050]In some embodiments, monomers contemplated for use to form the
electrically conductive polymer in the new composition comprise Formula I
below:

##STR00001##

[0051]wherein: [0052]Q is selected from the group consisting of S, Se,
and Te; [0053]R1 is independently selected so as to be the same or
different at each occurrence and is selected from hydrogen, alkyl,
alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl,
arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl,
alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl,
arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen,
nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl,
carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate,
ester sulfonate, and urethane; or both R1 groups together may form
an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered
aromatic or alicyclic ring, which ring may optionally include one or more
divalent nitrogen, selenium, tellurium, sulfur or oxygen atoms.

[0054]As used herein, the term "alkyl" refers to a group derived from an
aliphatic hydrocarbon and includes linear, branched and cyclic groups
which may be unsubstituted or substituted. The term "heteroalkyl" is
intended to mean an alkyl group, wherein one or more of the carbon atoms
within the alkyl group has been replaced by another atom, such as
nitrogen, oxygen, sulfur, and the like. The term "alkylene" refers to an
alkyl group having two points of attachment.

[0055]As used herein, the term "alkenyl" refers to a group derived from an
aliphatic hydrocarbon having at least one carbon-carbon double bond, and
includes linear, branched and cyclic groups which may be unsubstituted or
substituted. The term "heteroalkenyl" is intended to mean an alkenyl
group, wherein one or more of the carbon atoms within the alkenyl group
has been replaced by another atom, such as nitrogen, oxygen, sulfur, and
the like. The term "alkenylene" refers to an alkenyl group having two
points of attachment.

[0056]As used herein, the following terms for substituent groups refer to
the formulae given below: [0057]"alcohol" --R3--OH [0058]"amido"
--R3--C(O)N(R6)R6[0059]"amidosulfonate"
--R3--C(O)N(R6)R4--SO3Z [0060]"benzyl"
--CH2--C6H.sub.5 [0061]"carboxylate" --R3--C(O)O-Z or
--R3--O--C(O)-Z [0062]"ether"
--R3--(O--R5)p--O--R5[0063]"ether carboxylate"
--R3--O--R4--C(O)O-Z or --R3--O--R4--O--C(O)-Z
[0064]"ether sulfonate" --R3--O--R4--SO3Z [0065]"ester
sulfonate" --R3--O--C(O)--R4--SO3Z [0066]"sulfonimide"
--R3--SO2--NH--SO2--R5[0067]"urethane"
--R3--O--C(O)--N(R6)2[0068]where all "R" groups are the
same or different at each occurrence and: [0069]R3 is a single bond
or an alkylene group [0070]R4 is an alkylene group [0071]R5 is
an alkyl group [0072]R6 is hydrogen or an alkyl group [0073]p is 0
or an integer from 1 to 20 [0074]Z is H, alkali metal, alkaline earth
metal, N(R5)4 or R5 Any of the above groups may further be
unsubstituted or substituted, and any group may have F substituted for
one or more hydrogens, including perfluorinated groups. In some
embodiments, the alkyl and alkylene groups have from 1-20 carbon atoms.

[0075]In some embodiments, in the monomer, both R1 together form
--W--(CY1Y2)m--W--, where m is 2 or 3, W is O, S, Se, PO,
NR6, Y1 is the same or different at each occurrence and is
hydrogen or fluorine, and Y2 is the same or different at each
occurrence and is selected from hydrogen, halogen, alkyl, alcohol,
amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether
sulfonate, ester sulfonate, and urethane, where the Y groups may be
partially or fully fluorinated. In some embodiments, all Y are hydrogen.
In some embodiments, the polymer is poly(3,4-ethylenedioxythiophene). In
some embodiments, at least one Y group is not hydrogen. In some
embodiments, at least one Y group is a substituent having F substituted
for at least one hydrogen. In some embodiments, at least one Y group is
perfluorinated.

[0076]In some embodiments, the monomer has Formula I(a):

##STR00002##

[0077]wherein: [0078]Q is selected from the group consisting of S, Se, and
Te; [0079]R7 is the same or different at each occurrence and is
selected from hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl,
alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate,
ether sulfonate, ester sulfonate, and urethane, with the proviso that at
least one R7 is not hydrogen, and [0080]m is 2 or 3.

[0081]In some embodiments of Formula I(a), m is two, one R7 is an
alkyl group of more than 5 carbon atoms, and all other R7 are
hydrogen. In some embodiments of Formula I(a), at least one R7 group
is fluorinated. In some embodiments, at least one R7 group has at
least one fluorine substituent. In some embodiments, the R7 group is
fully fluorinated.

[0082]In some embodiments of Formula I(a), the R7 substituents on the
fused alicyclic ring on the monomer offer improved solubility of the
monomers in water and facilitate polymerization in the presence of the
fluorinated acid polymer.

[0083]In some embodiments of Formula I(a), m is 2, one R7 is sulfonic
acid-propylene-ether-methylene and all other R7 are hydrogen. In
some embodiments, m is 2, one R7 is propyl-ether-ethylene and all
other R7 are hydrogen. In some embodiments, m is 2, one R7 is
methoxy and all other R7 are hydrogen. In some embodiments, one
R7 is sulfonic acid difluoromethylene ester methylene
(--CH2--O--C(O)--CF2--SO3H), and all other R7 are
hydrogen.

[0084]In some embodiments, pyrrole monomers contemplated for use to form
the electrically conductive polymer in the new composition comprise
Formula II below.

##STR00003##

where in Formula II: [0085]R1 is independently selected so as to be
the same or different at each occurrence and is selected from hydrogen,
alkyl, alkenyl, alkoxy, alkanoyl, alkythio, aryloxy, alkylthioalkyl,
alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl,
alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl,
alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic
acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol,
benzyl, carboxylate, ether, amidosulfonate, ether carboxylate, ether
sulfonate, ester sulfonate, and urethane; or both R1 groups together
may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or
7-membered aromatic or alicyclic ring, which ring may optionally include
one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen
atoms; and [0086]R2 is independently selected so as to be the same
or different at each occurrence and is selected from hydrogen, alkyl,
alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino,
epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether
carboxylate, ether sulfonate, ester sulfonate, and urethane.

[0089]In some embodiments, the pyrrole monomer is unsubstituted and both
R1 and R2 are hydrogen.

[0090]In some embodiments, both R1 together form a 6- or 7-membered
alicyclic ring, which is further substituted with a group selected from
alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether
carboxylate, ether sulfonate, ester sulfonate, and urethane. These groups
can improve the solubility of the monomer and the resulting polymer. In
some embodiments, both R1 together form a 6- or 7-membered alicyclic
ring, which is further substituted with an alkyl group. In some
embodiments, both R1 together form a 6- or 7-membered alicyclic
ring, which is further substituted with an alkyl group having at least 1
carbon atom.

[0091]In some embodiments, both R1 together form
--O--(CHY)m--O--, where m is 2 or 3, and Y is the same or different
at each occurrence and is selected from hydrogen, alkyl, alcohol, benzyl,
carboxylate, amidosulfonate, ether, ether carboxylate, ether sulfonate,
ester sulfonate, and urethane. In some embodiments, at least one Y group
is not hydrogen. In some embodiments, at least one Y group is a
substituent having F substituted for at least one hydrogen. In some
embodiments, at least one Y group is perfluorinated.

[0092]In some embodiments, aniline monomers contemplated for use to form
the electrically conductive polymer in the new composition comprise
Formula III below.

##STR00004##

[0093]wherein:

[0094]a is 0 or an integer from 1 to 4;

[0095]b is an integer from 1 to 5, with the proviso that a+b=5; and

R1 is independently selected so as to be the same or different at
each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy,
alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino,
alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl,
alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl,
acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano,
hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether,
ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and
urethane; or both R1 groups together may form an alkylene or
alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or
alicyclic ring, which ring may optionally include one or more divalent
nitrogen, sulfur or oxygen atoms.

[0096]When polymerized, the aniline monomeric unit can have Formula IV(a)
or Formula IV(b) shown below, or a combination of both formulae.

##STR00005##

##STR00006##

where a, b and R1 are as defined above.

[0097]In some embodiments, the aniline monomer is unsubstituted and a=0.

[0098]In some embodiments, a is not 0 and at least one R1 is
fluorinated. In some embodiments, at least one R1 is perfluorinated.

[0099]In some embodiments, fused polycyclic heteroaromatic monomers
contemplated for use to form the electrically conductive polymer in the
new composition have two or more fused aromatic rings, at least one of
which is heteroaromatic. In some embodiments, the fused polycyclic
heteroaromatic monomer has Formula V:

##STR00007##

[0100]wherein: [0101]Q is S, Se, Te, or NR6; [0102]R6 is
hydrogen or alkyl; [0103]R8, R9, R10, and R11 are
independently selected so as to be the same or different at each
occurrence and are selected from hydrogen, alkyl, alkenyl, alkoxy,
alkanoyl, alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino,
alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl,
alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl,
acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile,
cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate,
ether, ether carboxylate, amidosulfonate, ether sulfonate, ester
sulfonate, and urethane; and [0104]at least one of R8 and R9,
R9 and R10, and R10 and R11 together form an
alkenylene chain completing a 5 or 6-membered aromatic ring, which ring
may optionally include one or more divalent nitrogen, sulfur, selenium,
tellurium, or oxygen atoms.

[0105]In some embodiments, the fused polycyclic heteroaromatic monomer has
a formula selected from the group consisting of Formula V(a), V(b), V(c),
V(d), V(e), V(f), V(g), V(h), V(i), V(j), and V(k):

##STR00008## ##STR00009##

[0106]wherein: [0107]Q is S, Se, Te, or NH; and [0108]T is the same or
different at each occurrence and is selected from S, NR6, O,
SiR62, Se, Te, and PR6; [0109]Y is N; and [0110]R6 is
hydrogen or alkyl.The fused polycyclic heteroaromatic monomers may be
further substituted with groups selected from alkyl, heteroalkyl,
alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate,
ester sulfonate, and urethane. In some embodiments, the substituent
groups are fluorinated. In some embodiments, the substituent groups are
fully fluorinated.

[0111]In some embodiments, the fused polycyclic heteroaromatic monomer is
a thieno(thiophene). Such compounds have been discussed in, for example,
Macromolecules, 34, 5746-5747 (2001); and Macromolecules, 35, 7281-7286
(2002). In some embodiments, the thieno(thiophene) is selected from
thieno(2,3-b)thiophene, thieno(3,2-b)thiophene, and
thieno(3,4-b)thiophene. In some embodiments, the thieno(thiophene)
monomer is further substituted with at least one group selected from
alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether
carboxylate, ether sulfonate, ester sulfonate, and urethane. In some
embodiments, the substituent groups are fluorinated. In some embodiments,
the substituent groups are fully fluorinated.

[0112]In some embodiments, polycyclic heteroaromatic monomers contemplated
for use to form the polymer in the new composition comprise Formula VI:

[0119]In some embodiments, the electrically conductive polymer is a
copolymer of a precursor monomer and at least one second monomer. Any
type of second monomer can be used, so long as it does not detrimentally
affect the desired properties of the copolymer. In some embodiments, the
second monomer comprises no more than 50% of the polymer, based on the
total number of monomer units. In some embodiments, the second monomer
comprises no more than 30%, based on the total number of monomer units.
In some embodiments, the second monomer comprises no more than 10%, based
on the total number of monomer units.

[0120]Exemplary types of second monomers include, but are not limited to,
alkenyl, alkynyl, arylene, and heteroarylene. Examples of second monomers
include, but are not limited to, fluorene, oxadiazole, thiadiazole,
benzothiadiazole, phenylenevinylene, phenyleneethynylene, pyridine,
diazines, and triazines, all of which may be further substituted.

[0121]In some embodiments, the copolymers are made by first forming an
intermediate precursor monomer having the structure A-B-C, where A and C
represent precursor monomers, which can be the same or different, and B
represents a second monomer. The A-B-C intermediate precursor monomer can
be prepared using standard synthetic organic techniques, such as
Yamamoto, Stille, Grignard metathesis, Suzuki, and Negishi couplings. The
copolymer is then formed by oxidative polymerization of the intermediate
precursor monomer alone, or with one or more additional precursor
monomers.

[0122]In some embodiments, the electrically conductive polymer is selected
from the group consisting of a polythiophene, a polypyrrole, a polymeric
fused polycyclic heteroaromatic, a copolymer thereof, and combinations
thereof.

[0123]In some embodiments, the electrically conductive polymer is selected
from the group consisting of poly(3,4-ethylenedioxythiophene),
unsubstituted polypyrrole, poly(thieno(2,3-b)thiophene),
poly(thieno(3,2-b)thiophene), and poly(thieno(3,4-b)thiophene).

b. Non-Fluorinated Polymeric Acid

[0124]Any non-fluorinated polymeric acid, which is capable of doping the
conductive polymer, can be used to make new compositions. Any polymer
having acidic groups with acidic protons can be used. The use of such
acids with conducting polymers such as polythiophenes, polyanilines and
polypyrroles is well known in the art. Examples of acidic groups include,
but are not limited to, carboxylic acid groups, sulfonic acid groups,
sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and
combinations thereof. The acidic groups can all be the same, or the
polymer may have more than one type of acidic group.

[0125]In one embodiment, the acid is a non-fluorinated polymeric sulfonic
acid. Some non-limiting examples of the acids are poly(styrenesulfonic
acid) ("PSSA"), poly(2-acrylamido-2-methyl-1-propanesulfonic acid)
("PAAMPSA"), and mixtures thereof.

[0126]The amount of non-fluorinated polymeric acid present is generally in
excess of that required to counterbalance the charge on the conducting
polymer. In some embodiments, the ratio of acid equivalents of
non-fluorinated polymeric acid to molar equivalents of conducting polymer
is in the range of 1-5.

[0127]The amount of doped conducting polymer in the composite dispersion
is generally at least 0.1 wt. %, based on the total weight of the
dispersion. In some embodiments, the wt. % is from 0.2 to 5.

3. SOLVENT

[0128]The solvent is a high-boiling, polar organic liquid. In some
embodiments, the solvent has a boiling point ("b.p.") of at least
120° C.; in some embodiments, at least 150° C. The solvent
is soluble in, miscible with, or dispersible in water. Examples of
solvents include, but are not limited to ethylene glycol,
dimethylsulfoxide, dimethylacetamide, and N-methylpyrrolidone. Mixtures
of solvents may also be used.

[0129]The solvent is generally present in the composite dispersion in the
amount of from 1 to 15 wt. %, based on the total weight of the
dispersion; in some embodiments, from 5 to 10 wt. %.

4. ADDITIVE

[0130]The additive is selected from the group consisting of carbon
fullerenes, nanotubes and combinations thereof.

[0131]Fullerenes are an allotrope of carbon characterized by a closed-cage
structure consisting of an even number of three-coordinate carbon atoms
devoid of hydrogen atoms. The fullerenes are well known and have been
extensively studied.

[0132]Examples of fullerenes include C60, C60-PCMB, and C70, shown below,

##STR00011##

as well as C84 and higher fullerenes. Any of the fullerenes may be
derivatized with a (3-methoxycarbonyl)-propyl-1-phenyl group ("PCBM"),
such as C70-PCBM, C84-PCBM, and higher analogs. Combinations of
fullerenes can be used.

[0133]In some embodiments, the fullerene is selected from the group
consisting of C60, C60-PCMB, C70, C70-PCMB, and combinations thereof.

[0134]Carbon nanotubes have a cylindrical shape. The nanotubes can be
single-walled or multi-walled. The materials are made by methods
including arc discharge, laser ablation, high pressure carbon monoxide,
and chemical vapor deposition. The materials are well known and
commercially available. In some embodiments, single-walled nanotubes are
used.

[0135]The amount of additive present is generally at least 0.2 wt. %,
based on the total weight of the dispersion. The weight ratio of
conductive polymer to additive is generally in the range of 0.5 to 50; in
some embodiments, the ratio is 1 to 10.

5. PREPARATION OF THE COMPOSITE DISPERSION

[0136]In the following discussion, the doped conductive polymer, solvent,
and additive will be referred to in the singular. However, it is
understood that more than one of any or all of these may be used.

[0137]The new electrically conductive polymer composition is prepared by
first forming the doped conductive polymer and then adding the solvent
and the additive, in any order.

[0138]The doped electrically conductive polymer is generally formed by
oxidative polymerization of the precursor monomer in the presence of the
non-fluorinated polymeric acid in an aqueous medium. Many of these
materials are commercially available. The additive can be dispersed in
water or a solvent/water mixture. These mixtures can then be added to an
aqueous dispersion of the doped conductive polymer, optionally with
additional solvent.

[0139]Alternatively, the additive can be added to the doped conductive
polymer dispersion directly as a solid. The solvent can be added to this
mixture.

[0140]In some embodiments, the pH is increased either prior to the
addition of the additive or after. The pH can be adjusted by treatment
with cation exchange resins, and/or base resins prior to additive
addition. In some embodiments, the pH is adjusted by the addition of
aqueous base solution. Cations for the base can be, but are not limited
to, alkali metal, alkaline earth metal, ammonium, and alkylammonium. In
some embodiments, alkali metal is preferred over alkaline earth metal
cations.

[0141]Films made from the composite aqueous dispersions described herein,
are hereinafter referred to as "the new films described herein". The
films can be made using any liquid deposition technique, including
continuous and discontinuous techniques. Continuous deposition
techniques, include but are not limited to, spin coating, gravure
coating, curtain coating, dip coating, slot-die coating, spray coating,
and continuous nozzle coating. Discontinuous deposition techniques
include, but are not limited to, ink jet printing, gravure printing, and
screen printing.

[0142]The films thus formed are smooth, relatively transparent, and can
have a conductivity greater than at least 100 S/cm.

7. BUFFER LAYERS

[0143]Organic light-emitting diodes (OLEDs) are an organic electronic
device comprising an organic layer capable of electroluminescence. OLEDs
can have the following configuration: [0144]anode/buffer layer/EL
material/cathodewith additional layers between the electrodes.
Electrically conducting polymers having low conductivity in the range of
10-3 to 10-7 S/cm are commonly used as the buffer layer in
direct contact with an electrically conductive, inorganic oxide anode
such as ITO. However, films of the new compositions having conductivity
greater than 100 S/cm can serve both anode and buffer layer functions.In
another embodiment of the invention, there are provided buffer layers
deposited from composite aqueous dispersions. The term "buffer layer" or
"buffer material" is intended to mean electrically conductive or
semiconductive materials and may have one or more functions in an organic
electronic device, including but not limited to, planarization of the
underlying layer, charge transport and/or charge injection properties,
scavenging of impurities such as oxygen or metal ions, and other aspects
to facilitate or to improve the performance of the organic electronic
device. The term "layer" is used interchangeably with the term "film" and
refers to a coating covering a desired area. The term is not limited by
size. The area can be as large as an entire device or as small as a
specific functional area such as the actual visual display, or as small
as a single sub-pixel. Layers and films can be formed by any conventional
deposition technique, including vapor deposition, liquid deposition
(continuous and discontinuous techniques), and thermal transfer.
Continuous deposition techniques, include but are not limited to, spin
coating, gravure coating, curtain coating, dip coating, slot-die coating,
spray coating, and continuous nozzle coating. Discontinuous deposition
techniques include, but are not limited to, ink jet printing, gravure
printing, and screen printing.

8. ELECTRONIC DEVICES

[0145]The new films described herein can be used in electronic devices
where the high conductivity is desired in combination with transparency.
In some embodiments, the films are used as electrodes. In some
embodiments, the films are used as transparent conductive coatings.

[0146]In another embodiment of the invention, there are provided
electronic devices comprising at least one electroactive layer positioned
between two electrical contact layers, wherein the device further
includes the new buffer layer. The term "electroactive" when referring to
a layer or material is intended to mean a layer or material that exhibits
electronic or electro-radiative properties. An electroactive layer
material may emit radiation or exhibit a change in concentration of
electron-hole pairs when receiving radiation.

[0148]The device may include a support or substrate (not shown) that can
be adjacent to the anode layer 110 or the cathode layer 160. Most
frequently, the support is adjacent to the anode layer 110. The support
can be flexible or rigid, organic or inorganic. Examples of support
materials include, but are not limited to, glass, ceramic, metal, and
plastic films.

[0149]The anode layer 110 is an electrode that is more efficient for
injecting holes compared to the cathode layer 160. The new films of this
invention described herein are particularly suitable as the anode layer
because of their high conductivity. In some embodiments, they have a
conductivity of 100 S/cm or greater. In some embodiments, they have a
conductivity of 200 S/cm or greater. They are deposited onto substrates
using a variety of techniques well-known to those skilled in the art.
Typical deposition techniques include liquid deposition (continuous and
discontinuous techniques), and thermal transfer.

[0150]In some embodiments, the new films described herein are used alone
as an anode without optional buffer layer 120. In this embodiment, the
new films of this invention serve the functions of both anode layer and
buffer layer.

[0151]In some embodiments, the new films described herein are used as the
top layer in a bilayer or multilayer anode. The other anode layers can
include materials containing a metal, mixed metal, alloy, metal oxide or
mixed oxide. Suitable materials include the mixed oxides of the Group 2
elements (i.e., Be, Mg, Ca, Sr, Ba, Ra), the Group 11 elements, the
elements in Groups 4, 5, and 6, and the Group 8-10 transition elements.
If the anode layer 110 is to be light transmitting, mixed oxides of
Groups 12, 13 and 14 elements, such as indium-tin-oxide, may be used. As
used herein, the phrase "mixed oxide" refers to oxides having two or more
different cations selected from the Group 2 elements or the Groups 12,
13, or 14 elements. Some non-limiting, specific examples of materials for
anode layer 110 include, but are not limited to, indium-tin-oxide
("ITO"), indium-zinc-oxide, aluminum-tin-oxide, gold, silver, copper, and
nickel. The mixed oxide layer may be formed by a chemical or physical
vapor deposition process or spin-cast process. Chemical vapor deposition
may be performed as a plasma-enhanced chemical vapor deposition ("PECVD")
or metal organic chemical vapor deposition ("MOCVD"). Physical vapor
deposition can include all forms of sputtering, including ion beam
sputtering, as well as e-beam evaporation and resistance evaporation.
Specific forms of physical vapor deposition include rf magnetron
sputtering and inductively-coupled plasma physical vapor deposition
("IMP-PVD"). These deposition techniques are well known within the
semiconductor fabrication arts.

[0152]In one embodiment, the mixed oxide layer is patterned. The pattern
may vary as desired. The layers can be formed in a pattern by, for
example, positioning a patterned mask or resist on the first flexible
composite barrier structure prior to applying the first electrical
contact layer material. Alternatively, the layers can be applied as an
overall layer (also called blanket deposit) and subsequently patterned
using, for example, a patterned resist layer and wet chemical or dry
etching techniques. Other processes for patterning that are well known in
the art can also be used.

[0153]Optional buffer layer 120 may be present adjacent to the anode layer
110. The term "buffer layer" or "buffer material" is intended to mean
electrically conductive or semiconductive materials having conductivity
usually in the range between 10-3 to 10-7 S/cm, but higher
conductivity can be used for some device geometries. The buffer layer may
have one or more functions in an organic electronic device, including but
not limited to, planarization of the underlying layer, charge transport
and/or charge injection properties, scavenging of impurities such as
oxygen or metal ions, and other aspects to facilitate or to improve the
performance of the organic electronic device.

[0154]In some embodiments, the buffer layer 120 comprises the new film
described herein, where the conductivity is 100 S/cm or less.

[0156]Depending upon the application of the device, the electroactive
layer 140 can be a light-emitting layer that is activated by an applied
voltage (such as in a light-emitting diode or light-emitting
electrochemical cell), a layer of material that responds to radiant
energy and generates a signal with or without an applied bias voltage
(such as in a photodetector). In one embodiment, the electroactive
material is an organic electroluminescent ("EL") material, Any EL
material can be used in the devices, including, but not limited to, small
molecule organic fluorescent compounds, fluorescent and phosphorescent
metal complexes, conjugated polymers, and mixtures thereof. Examples of
fluorescent compounds include, but are not limited to, pyrene, perylene,
rubrene, coumarin, derivatives thereof, and mixtures thereof. Examples of
metal complexes include, but are not limited to, metal chelated oxinoid
compounds, such as tris(8-hydroxyquinolate)aluminum (Alq3);
cyclometallated iridium and platinum electroluminescent compounds, such
as complexes of iridium with phenylpyridine, phenylquinoline, or
phenylpyrimidine ligands as disclosed in Petrov et al., U.S. Pat. No.
6,670,645 and Published PCT Applications WO 03/063555 and WO 2004/016710,
and organometallic complexes described in, for example, Published PCT
Applications WO 03/008424, WO 03/091688, and WO 03/040257, and mixtures
thereof. Electroluminescent emissive layers comprising a charge carrying
host material and a metal complex have been described by Thompson et al.,
in U.S. Pat. No. 6,303,238, and by Burrows and Thompson in published PCT
applications WO 00/70655 and WO 01/41512. Examples of conjugated polymers
include, but are not limited to poly(phenylenevinylenes), polyfluorenes,
poly(spirobifluorenes), polythiophenes, poly(p-phenylenes), copolymers
thereof, and mixtures thereof.

[0157]Optional layer 150 can function both to facilitate electron
injection/transport, and can also serve as a confinement layer to prevent
quenching reactions at layer interfaces. More specifically, layer 150 may
promote electron mobility and reduce the likelihood of a quenching
reaction if layers 140 and 160 would otherwise be in direct contact.
Examples of materials for optional layer 150 include, but are not limited
to, metal chelated oxinoid compounds, such as
bis(2-methyl-8-quinolinolato)(para-phenyl-phenolato)aluminum(III) (BAIQ)
and tris(8-hydroxyquinolato)aluminum (Alq3);
tetrakis(8-hydroxyquinolinato)zirconium; azole compounds such as
2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD),
3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and
1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivatives
such as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthroline derivatives
such as 9,10-diphenylphenanthroline (DPA) and
2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and any one or more
combinations thereof. Alternatively, optional layer 150 may be inorganic
and comprise BaO, LiF, Li2O, or the like.

[0158]The cathode layer 160 is an electrode that is particularly efficient
for injecting electrons or negative charge carriers. The cathode layer
160 can be any metal or nonmetal having a lower work function than the
first electrical contact layer (in this case, the anode layer 110). As
used herein, the term "lower work function" is intended to mean a
material having a work function no greater than about 4.4 eV. As used
herein, "higher work function" is intended to mean a material having a
work function of at least approximately 4.4 eV.

[0159]Materials for the cathode layer can be selected from alkali metals
of Group 1 (e.g., Li, Na, K, Rb, Cs), the Group 2 metals (e.g., Mg, Ca,
Ba, or the like), the Group 12 metals, the lanthanides (e.g., Ce, Sm, Eu,
or the like), and the actinides (e.g., Th, U, or the like). Materials
such as aluminum, indium, yttrium, and combinations thereof, may also be
used. Specific non-limiting examples of materials for the cathode layer
160 include, but are not limited to, barium, lithium, cerium, cesium,
europium, rubidium, yttrium, magnesium, samarium, and alloys and
combinations thereof.

[0160]The cathode layer 160 is usually formed by a chemical or physical
vapor deposition process. In some embodiments, the cathode layer will be
patterned, as discussed above in reference to the anode layer 110.

[0161]Other layers in the device can be made of any materials which are
known to be useful in such layers upon consideration of the function to
be served by such layers.

[0162]In some embodiments, an encapsulation layer (not shown) is deposited
over the contact layer 160 to prevent entry of undesirable components,
such as water and oxygen, into the device 100. Such components can have a
deleterious effect on the organic layer 140. In one embodiment, the
encapsulation layer is a barrier layer or film. In one embodiment, the
encapsulation layer is a glass lid.

[0163]Though not depicted, it is understood that the device 100 may
comprise additional layers. Other layers that are known in the art or
otherwise may be used. In addition, any of the above-described layers may
comprise two or more sub-layers or may form a laminar structure.
Alternatively, some or all of anode layer 110, the buffer layer 120, the
hole transport layer 130, the electron transport layer 150, cathode layer
160, and other layers may be treated, especially surface treated, to
increase charge carrier transport efficiency or other physical properties
of the devices. The choice of materials for each of the component layers
is preferably determined by balancing the goals of providing a device
with high device efficiency with device operational lifetime
considerations, fabrication time and complexity factors and other
considerations appreciated by persons skilled in the art. It will be
appreciated that determining optimal components, component
configurations, and compositional identities would be routine to those of
ordinary skill of in the art.

[0164]In one embodiment, the different layers have the following range of
thicknesses: anode 110, 500-5000 Å, in one embodiment 1000-2000
Å; optional buffer layer 120, 50-2000 Å, in one embodiment
200-1000 Å; optional hole transport layer 130, 50-2000 Å, in one
embodiment 100-1000 Å; photoactive layer 140, 10-2000 Å, in one
embodiment 100-1000 Å; optional electron transport layer 150, 50-2000
Å, in one embodiment 100-1000 Å; cathode 160, 200-10000 Å, in
one embodiment 300-5000 Å. The location of the electron-hole
recombination zone in the device, and thus the emission spectrum of the
device, can be affected by the relative thickness of each layer. Thus the
thickness of the electron-transport layer should be chosen so that the
electron-hole recombination zone is in the light-emitting layer. The
desired ratio of layer thicknesses will depend on the exact nature of the
materials used.

[0165]In operation, a voltage from an appropriate power supply (not
depicted) is applied to the device 100. Current therefore passes across
the layers of the device 100. Electrons enter the organic polymer layer,
releasing photons. In some OLEDs, called active matrix OLED displays,
individual deposits of photoactive organic films may be independently
excited by the passage of current, leading to individual pixels of light
emission. In some OLEDs, called passive matrix OLED displays, deposits of
photoactive organic films may be excited by rows and columns of
electrical contact layers.

[0166]Although methods and materials similar or equivalent to those
described herein can be used in the practice or testing of the present
invention, suitable methods and materials are described below. All
publications, patent applications, patents, and other references
mentioned herein are incorporated by reference in their entirety. In case
of conflict, the present specification, including definitions, will
control. In addition, the materials, methods, and examples are
illustrative only and not intended to be limiting.

[0167]It is to be appreciated that certain features of the invention which
are, for clarity, described above and below in the context of separate
embodiments, may also be provided in combination in a single embodiment.
Conversely, various features of the invention that are, for brevity,
described in the context of a single embodiment, may also be provided
separately or in any subcombination. Further, reference to values stated
in ranges include each and every value within that range.

EXAMPLES

A) General Procedure of Film Sample Preparation, Four-Probe Electrical
Resistance Measurement and Calculation of Electrical Conductivity

[0168]One small drop of each dispersion sample was placed on a
3''×1'' microscope slide placed on a hot plate set at
˜170° C. in air. The liquid was spread with a small diameter
(˜1 mm) glass rod to form a thin film on 2/3 area of the slide as
the liquid was evaporating. The slide was removed from the hot plate and
the film was trimmed to a long strip with a razor blade. Width of the
strip ranged from 0.2 cm to 0.7 cm and the length was about 3 cm. The
microscope slide containing the strip was then placed on a hot plate set
at 210° C. for 10 minutes. Once cooled to room temperature, silver
paste was then painted perpendicular to the length of the strip to form
four electrodes. The two inner parallel electrodes were about 0.3 cm to
0.5 cm apart and were connected to a Keithley model 616 electrometer for
measurement of voltage. The two outside parallel electrodes were
connected to a Keithley model 225 Current Supplier. A series of
corresponding current/voltage data obtained at room temperature was
recorded to see whether Ohm's law was followed. All the samples in the
Examples followed Ohm's law, which provided a more or less identical
resistance of the corresponding current/voltage data. Once resistance
measurement was done, the area in the two inner electrodes was measured
for thickness with a Profilometer. Thickness of the tested films is
typically in the range of 1 micrometer (um). Since resistance, thickness,
separation length of the two inner electrodes and the width of the
filmstrip are known, electrical conductivity is then calculated. The
conductivity unit is expressed as S (Siemens)/cm.

[0170]CNT used in this example was HIPco CE608, purchased from CNI (Carbon
Nanotechnologies, Inc.) at Houston, Tex., USA. HIPco CE608 CNT is single
wall nanotubes, which contains about 3-4% (w/w) residual catalyst. It was
made by a process using high-pressure carbon monoxide and then purified
by the Company.

[0171]Electrically conducting polymer used in this example is
poly(3,4-ethylenedioxythiophene) doped with non-fluorinated doping acid
poly(styrenesulfonic acid), abbreviated as "PEDOT/PSSA". PEDOT/PSSA is a
well-known electrically conductive polymer. The polymer dispersed in
water is commercially available from H. C. Starck GmbH (Leverkuson,
Germany) in several grades under a trade name of Baytron-P. Baytron-P
HCV4, one of the commercial aqueous dispersion products, purchased from
Starck was used. The Baytron-P HCV4 sample was determined gravimetrically
to have 1.01% (w/w) solid, which should be PEDOT/PSSA in water. According
to the product brochure, the weight ratio of PEDOT:PSSA is 1:2.5.

[0172]Prior to preparation of a CNT composite dispersion, an ethylene
glycol/water solution was prepared. The solution was for reducing
PEDOT-PSSA solid % of HCV4, therefore reducing its viscosity. A 19.93%
(w/w) ethylene glycol/water solution was made by adding 3.9988 g ethylene
glycol to 16.0610 g deionized water.

[0173]0.0876 g CNT were first placed in a glass jug. To the CNT solids,
14.7193 g ethylene glycol (19.93%, w/w)/water solution were added,
followed with 13.9081 g Baytron-P HCV4. Based on the quantity of each
component, the mixture contains 0.49% (w/w) PEDOT-PSSA, 10.22% (w/w)
ethylene glycol, 0.31% (w/w) CNT, and the remaining is water. The mixture
was subjected to sonication for 15 minutes continuously using a Branson
Model 450 Sonifier having power set at #4. The glass jug was immersed in
ice water contained in a tray to remove heat produced from intense
cavitation during entire period of sonication. The mixture formed a
smooth, stable dispersion without any sign of sedimentation. PH of the
dispersion was measured to be 2.1 using a pH meter (model 63) from Jenco
Electronics, Ltd (San Diego, Calif.).

[0174]Films were prepared according to the general procedure described in
thin film preparation. Thin films are optically transmissive and stronger
mechanically than those of the conducting polymer without CNT. Thin films
were tested for electrical conductivity as described in the general
procedure. The conductivity of five film samples at room temperature was
measured to be 509.3 S/cm, 667.3 S/cm, 441.3 S/cm, 546.8 S/cm, and 551.2
S/cm.

Example 2

[0175]This example illustrates addition of a base solution on stability of
the composite dispersion prepared in Example 1.

[0176]About 10 g of the dispersion sample made in Example 1 was first
adjusted to pH3.9 using 0.5N NaOH/water solution first and then 0.1N
NaOH/water as pH got closer to the targeted pH. One half of the pH3.9
dispersion was further adjusted to pH7.0 with sodium hydroxide/water
solution too. Concentration of each component in the dispersions was not
significantly affected because only a very small amount of base solution
was used. Addition of the base solution still maintains homogeneity of
the dispersion. There is no sign of sedimentation in both high pH
dispersions. The high pH dispersions also form homogeneous films.

Example 3

[0177]This example illustrates preparation and film conductivity of a
stable aqueous dispersion containing a different carbon nanotube (CNT),
electrically conducting polymer, and a high boiling organic liquid.

[0178]CNT used in this example was HIPco P0244, also purchased from CNI
(Carbon Nanotechnologies, Inc.) at Houston, Tex., USA. HIPco P0244 CNT is
single wall nanotubes, which contains about 10% (w/w) residual catalyst.
It was made by a process using high-pressure carbon monoxide and then
purified by the Company. Electrically conducting polymer used in this
example is also Baytron-P HCV4. This lot of sample was determined
gravimetrically to have 1.1% (w/w) solid, which should be PEDOT/PSSA in
water. According to the product brochure, the weight ratio of PEDOT:PSSA
is 1:2.5.

[0179]Prior to preparation of a CNT composite dispersion, an ethylene
glycol/water solution was prepared. The solution was for reducing
PEDOT-PSSA solid % of HCV4, therefore reducing its viscosity. A 18.01%
(w/w) ethylene glycol/water solution was made by adding 3.6035 g ethylene
glycol to 16.4057 g deionized water.

[0180]0.0981 g CNT were first placed in a glass jug. To the CNT solids,
17.2521 g ethylene glycol (18.01%, w/w)/water solution were added,
followed with 15.5701 g Baytron-P HCV4. Based on the quantity of each
component, the mixture contains 0.52% (w/w) PEDOT-PSSA, 9.44% (w/w)
ethylene glycol, 0.298% (w/w) CNT, and the remaining is water. The
mixture was subjected to sonication for 28 minutes continuously using a
Branson Model 450 Sonifier having power set at #4. The glass jug was
immersed in ice water contained in a tray to remove heat produced from
intense cavitation during entire period of sonication. The mixture formed
a smooth, stable dispersion without any sign of sedimentation. pH of the
dispersion was measured to be 2.0 using a pH meter (model 63) from Jenco
Electronics, Ltd (San Diego, Calif.).

[0181]Films were prepared according to the general procedure described in
thin film preparation. Thin films are optically transmissive and stronger
mechanically than those of the conducting polymer without CNT. Thin films
were tested for electrical conductivity as described in the general
procedure. The conductivity of six film samples at room temperature was
measured to be 608.7 S/cm, 459.3 S/cm, 366.6 S/cm, 528.8 S/cm, 481.0
S/cm, and 472.3 S/cm.

[0182]Note that not all of the activities described above in the general
description or the examples are required, that a portion of a specific
activity may not be required, and that one or more further activities may
be performed in addition to those described. Still further, the order in
which activities are listed are not necessarily the order in which they
are performed.

[0183]In the foregoing specification, the concepts have been described
with reference to specific embodiments. However, one of ordinary skill in
the art appreciates that various modifications and changes can be made
without departing from the scope of the invention as set forth in the
claims below. Accordingly, the specification and figures are to be
regarded in an illustrative rather than a restrictive sense, and all such
modifications are intended to be included within the scope of invention.

[0184]Benefits, other advantages, and solutions to problems have been
described above with regard to specific embodiments. However, the
benefits, advantages, solutions to problems, and any feature(s) that may
cause any benefit, advantage, or solution to occur or become more
pronounced are not to be construed as a critical, required, or essential
feature of any or all the claims.

[0185]It is to be appreciated that certain features are, for clarity,
described herein in the context of separate embodiments, may also be
provided in combination in a single embodiment. Conversely, various
features that are, for brevity, described in the context of a single
embodiment, may also be provided separately or in any subcombination.

[0186]The use of numerical values in the various ranges specified herein
is stated as approximations as though the minimum and maximum values
within the stated ranges were both being preceded by the word "about." In
this manner slight variations above and below the stated ranges can be
used to achieve substantially the same results as values within the
ranges. Also, the disclosure of these ranges is intended as a continuous
range including every value between the minimum and maximum average
values including fractional values that can result when some of
components of one value are mixed with those of different value.
Moreover, when broader and narrower ranges are disclosed, it is within
the contemplation of this invention to match a minimum value from one
range with a maximum value from another range and vice versa.